The role of electronic factors in reagents in controlling thestereochemistry of arylsulfenyl chlorides addition

For a series of substituted arylsulfenyl chlorides the stereochemistry of Ad_E-reactions with a series of substituted Z- and E-β-deuterostyrenes has been elucidated. Non-stereospecific reaction was observed only for the pair 2,4-dinitrobenzenesulfenyl chloride-p-methoxystyrene; for all the other reactants the reaction proceeded in a strictly stereospecific manner.     

Investigation of the reduction of methylenequinones by methods of polarography and EPR spectroscopy

Conclusions The polarographic reduction of certain methylenequinones was studied, and the mechanism of the reduction was investigated by the method of EPR spectroscopy.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1656–1658, July, 1970.     

EPR spectra of halogenonitromethane anion radicals

Conclusions It was deduced that fluorine is in a -combined state in the anion radicals we studied; this was based on an analysis of the EPR spectra of a series of fluoronitroalkane anion radicals.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 458–460, February, 1969.In conclusion, the authors express their appreciation to A. A. Fainzil'berg for his interest in our work.     

Mechanism of Dehydrobromination of 1,2-Dibromo-1-phenylethane under Conditions of Phase-Transfer Catalysis

Selective dehydrobromination of 1,2-dibromo-1-phenylethane to -bromostyrene was effected under conditions of phase-transfer catalysis in systems containing KOH, toluene, and tetraalkylammonium bromides. The high selectivity of the catalytic systems originates from stabilization by lipophilic cation of the phase-transfer catalyst of a E1cb-like transition state in the E2 mechanism. In the presence of a catalytic amount of lipophilic alcohols, phenylacetylene was obtained. Substrate activation by alcohol molecules is explained by enhancement of the acceptor power of halogen atoms due to solvation and by increased mobility of hydrogen atoms.     

New Procedure for Determining the Solubility of Lypophilic Nonionic Surfactants in Water

The procedure that allows to study the kinetics of a dissolution of oleophilic nonionic surfactants in water and to determine the equilibrium values of solubility (S ^eq _w) was proposed, based on the spectrophotometry of extremely dilute, finely dispersed o/w emulsions of these substances prepared by sonication. The equilibrium values of solubility of tetraethoxylated p-nonylphenol (Neonol AF_9-4) and sorbitan monolaurate (Span-20) at 293 K in water are 3.67 × 10^–5 and 1.03 × 10^–5 M, respectively. For the tetraethoxylated p-nonylphenol, the equilibrium value of solubility in water determined by the proposed procedure agrees well with that determined by precision tensiometric measurements.     

Hydrodynamic and conformational properties of cellulose myristate molecules in solution

Cellulose myristate samples with a degree of substitution of 230–250 have been studied by the methods of molecular hydrodynamics (viscometry, analytical ultracentrifugation (flotation), and isothermal translational diffusion) in chloroform in the range M = (56–652) × 10³. The experimental evidence has been interpreted within the framework of the generalized wormlike Yamakawa-Fuji model with the following parameters: the persistence length a = 115 × 10^?8 cm, the chain diameter d = 45 × 10^?8 cm, and the molecular mass per unit chain length M _L = 270 × 10⁸ cm^?1. It has been inferred that the polymer dissolves in chloroform in the form of dimers.     

Classification of heavy-metal fluorides. fluorides with fluorite-like cation arrangement

The main feature of fluorite structure type is four families of crystallographic planes with dense trigon cation nets which are mutually oriented as the faces of a regular octahedron. A complicated cation composition may cause lowering of general symmetry to tetragonal (only one four-fold axis remains in the octahedral complex), rhombohedral (one three-fold axis), orthorhombic, and monoclinic. The geometric parameters of the cation sublattice remain constant. They are close to the parameters of the ideal face-centered cubic cation sublattice of fluorite (the measure of similarity is 1.00–0.81). This is true for all analyzed fluoride structures and some U⁴⁺, Th⁴⁺, Zr, and Ln oxyfluorides. Thus, the concept is confirmed that the crystalline state is determined by systems of parallel planes filled by dense heavy-atom nets. Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Institute of Crystallography, Russian Academy of Sciences. Translated fromZhurnal Struktumoi Khimii, Vol. 35, No. 1, pp. 71–80, January–February, 1994. Translated by T. Yudanova